(Thiono) (thiol) phosphoric (phosphonic) acid esters and ester-amides of substituted 4-hydroxyquinolines and their use as agents for combating pests

ABSTRACT

Phosphoric and phosphonic acid derivatives of substituted 4-hydroxyquinolines of the formula ##STR1## in which R 1  denotes alkyl, alkoxy, alkylthio, (di)alkylamino or phenyl, R 2  and R 4  denote alkyl, R 3  denotes H, halogen, carbalkoxy, substituted carbonamido or CN, R 5  denotes H, halogen, NO 2 , alkyl, alkoxy or CF 3  and X denotes O or S, are effective insecticides and fungicides.

The invention relates to compounds of the formula I ##STR2## in which R¹denotes (C₁ -C₄)-alkyl, (C₁ -C₄)-alkoxy, (C₁ -C₄)-alkylthio, (C₁-C₄)-alkylamino, (C₁ -C₄)-dialkylamino or phenyl, R² denotes (C₁-C₄)-alkyl, R³ denotes hydrogen, halogen, COOalkyl, CONH(alkyl) orCON(alkyl)₂ with in each case 1-4 C atoms per alkyl radical, or CN, R⁴denotes (C₁ -C₄)-alkyl, R⁵ denotes hydrogen, halogen, nitro, (C₁-C₄)-alkyl, (C₁ -C₄)-alkoxy or trihalogenomethyl and X denotes oxygen orsulfur.

Here and in the text which follows, "halogen" preferably denotesfluorine, chlorine or bromine, in particular chlorine.

The invention also relates to a process for the preparation of compoundsof the formula I, which comprises reacting 4-hydroxyquinolines of thegeneral formula II ##STR3## in which R³, R⁴ and R⁵ have the meaningsgiven under the general formula I, with (thiono) (thiol) phosphoric(phosphonic) acid ester chlorides or ester-amide chlorides of thegeneral formula III ##STR4## in which R¹, R² and X have the meaningsgiven under the general formula I, in the presence of acid-bindingagents.

The reactions are advantageously carried out in a solvent which is inertunder the reaction conditions, such as, for example, a lower ketone,acetonitrile, dimethylformamide, dimethylsulfoxide, glycoldimethylether,diisopropylether, benzene, toluene, xylene, chlorobenzene, ethyl acetateor dichloroethane, at temperatures between room temperature and theboiling point of the solvent used, preferably at 40°-90° C. It isnecessary to add an acid-binding agent in order to bind the hydrogenchloride liberated. Acid-binding agents which can advantageously be usedare alkali alcoholates or carbonates or organic bases, such as pyridineor triethylamine. The 4-hydroxyquinolines of the general formula II usedas the starting material have already been described in some cases, orthey can be prepared by methods which are known from the literature [forexample J. Y. Merour et al, Synthesis 1978, pages 698-700]. The (thiono)(thiol) phosphoric (phosphonic) acid ester chlorides and esteramidechlorides of the general formula III employed are known and can beprepared by customary processes [Houben-Weyl, Vol. XII/1, page 560; Vol.XII/2, pages 274, 607, 621, 755; and Soviet Union Patent SpecificationNo. 184,863]. The compounds of the formula I are distinguished by a goodacaricidal and insecticidal activity. The latter is directed bothtowards sucking and towards biting insects.

The sucking insects which can be combated with the compounds accordingto the invention include, for example, aphids (Aphididae), such as thegreen peach aphid (Myzus persicae) and the black bean aphid (Doralisfabae), courpea aphid (Aphis craccivora), the bird cherry aphid(Rhopalosiphum padi), the pea aphid (Macrosiphum pisi) and the potatoaphid (Macrosiphum solanifolii), as well as the current gall aphid(Cryptomyzus korschelti), the rosy apple aphid (Sappaphis mali), themealy plum aphid (Hyalopterus arundinis) and the cherry black-fly (Myzuscerasi); thrips (Thysanoptera), such as Hercinothrips femoralis, andbugs, for example the beet bug (Piesma quadrata), the red cotton bug(Dysdercus intermedius, Oncopeltus fasciatus), the bed bug (Cimexlectularius), the assassin bug (Rhodnius prolixus) and Chagas' bug(Triatoma infestans) and furthermore cicadas, such as Euscelis bilobatusand Nephotettix bipunctatus.

The following biting insects should be mentioned: butterfly caterpillars(Lepidoptera) such as the diamond-back moth (Plutella maculipennis), thegipsy moth (Lymantria dispar), the brown-tail moth (Euproctischrysorrhoea) and the tent caterpillar (Malacosoma neustria), and alsothe cabbage moth (Mamestra brassicae) and the cutworm (Agrotis segetum),the large white butterfly (Pieris brassicae), the small winter moth(Cheimatobia brumata), the green oak tortrix moth (Tortrix viridana),the fall armyworm (Laphygma frugiperda) and cotton worm (Prodenialitura), and the ermine moth (Hyponomeuta padella), the Mediterraneanflour moth (Ephestia kuhniella) and the greater wax moth (Galleriamellonella).

The biting insects also include beetles (Coleoptera), for example thegranary weevil (Calandra granaria), the Colorado beetle (Leptinotarsadecemlineata), the blossom beetle (Meligethes aeneus), the raspberrybeetle (Byturus tomentosus), the bean weevil (Acanthoscelides obtectus),the leather beetle (Dermestes frischi), the khapra beetle (Trogodermagranarium), the flour beetle (Tribolium castaneum), the northern cornbillbug (Sitophilus zeamais), the drugstore beetle (Stegobium paniceum),the yellow mealworm (Tenebrio molitor) and the saw-toothed grain beetle(Oryzaephilus surinamensis); cockroaches, such as the German cockroach(Blatella germanica), the American cockroach (Periplaneta americana),the Madeira cockroach (Leucophaea maderae), the oriental cockroach(Blatta orientalis), the giant cockroach (Blaberus giganteus) and theblack giant cockroach (Blaberus fuscus); and also Orthoptera, forexample the house cricket (Acheta domesticus).

The Diptera comprise essentially flies, such as the vinegar fly(Drosophila melanogaster), the Mediterranean fruit fly (Ceratitiscapitata), the house fly (Musca domestica), the little house fly (Fanniacanicularis), the black blow-fly (Phormia aegina) and the bluebottle fly(Calliphora erythrocephala) as well as the stable fly (Stomoxyscalcitrans); and also gnats, for example mosquitoes, such as the yellowfever mosquito (Aedes aegypti), the northern house mosquito (Culexpipiens) and the malaria mosquito (Anopheles stephensi).

The mites (Acari) include, in particular, the spider mites(Tetranychidae) such as the two-spotted spider mite (Tetranychusurticae) and the European red mite (Panonychus ulmi), gall mites, forexample the blackcurrant gall mite (Eriophyes ribis), and tarsonemids,for example the broad mite (Hemitarsonemus latus) and the cyclamen mite(Tarsonemus pallidus).

When used against hygiene pests and pests of stored products, inparticular flies and gnats, the process products also exhibit anoutstanding residual action on wood and clay.

Moreover, the compounds claimed have a very good fungicidal, and in somecases systemic, action against phytopathogenic fungi and are thereforeoutstandingly suitable as plant protection agents. The compoundsprevent, for example, Phytophthora infestans, Plasmopara viticola,Pythium ultimum, Venturia inaequalis, Rhizoctonia solani and powderymildew fungi. They have an excellent fungicidal action againstPiricularia oryzae and various rust fungi.

The invention thus also relates the acaricidal, insecticidal andfungicidal agents, which, in addition to the customary formulationauxiliaries and inert substances, contain compounds of the formula I,and to the use of the compounds for combating acaridae, insects andphytopathogenic fungi.

The agents according to the invention generally contain the activecompounds of the formula I in amounts of 1-95% by weight. They can beused as wettable powders, emulsifiable concentrates, solutions which canbe sprayed, dusting agents or granules, in the customary formulations.

Wettable powders are products which can be uniformly dispersed in waterand which, in addition to the active compound and as well as a diluentor inert substance, also contain wetting agents, for examplepolyoxyethylated alkyl phenols, polyoxyethylated fatty alcohols andalkyl- or alkylphenyl-sulfonates, and dispersing agents, for examplesodium lignin-sulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate,sodium dibutylnapthalenesulfonate,or sodium oleyl-methyl-taurate.

Emulsifiable concentrates are prepared by dissolving the active compoundin an organic solvent, for example butanol, cyclohexanone,dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons,with the addition of one or more emulsifiers. Examples of emulsifierswhich can be used are: calcium alkylarylsulfonates, such asCadodecylbenzenesulfonate, or non-ionic emulsifiers, such as fatty acidpolyglycol esters, alkylarylpolyglycol ethers, fatty alcohol polyglycolethers, propylene oxide/ethylene oxide condensation products, fattyalcohol/propylene oxide/ethylene oxide condensation products, alkylpolyethers, sorbitane fatty acid esters, polyoxyethylene sorbitane fattyacid esters or polyoxyethylene sorbital esters.

Dusting agents are obtained by grinding the active compound with finelydivided solid substances, for example talc or natural clays, such askaolin, bentonite, pyrophillite or diatomaceous earth. Granules can beprepared either by atomizing the active compound onto an absorbent,granular inert material, or applying active compound concentrates to thesurface of carriers, such as sand or kaolinites, or of a granular inertmaterial, by means of adhesives, for example polyvinyl alcohol, sodiumpolyacrylate or mineral oils. Suitable active compounds can also beformulated in the manner customary for the preparation of fertilizergranules--if desired as mixtures with fertilizers.

The active compound concentration in wettable powders varies, forexample, between about 10% and 80%, the remainder consisting of theabovementioned formulation additives. The active compound concentrationin emulsifiable concentrates can likewise be about 10% to 80%. Dust-likeformulations contain at most 5-20% of active compound, and solutionswhich can be sprayed contain about 2-20%. In the case of granules, theactive ingredient content partly depends on whether the active compoundis liquid or solid, and which granulation auxiliaries, fillers and thelike are used.

For use, the commercially available concentrates are diluted, ifappropriate, in the customary manner, for example by means of water inthe case of wettable powders and emulsifiable concentrates. Theready-to-spray suspensions preferably contain 0.05 to 2%, in particular0.1 to 1%, of active compound. Dust-like and granular formulations, andsolutions which can be sprayed are not diluted more with further inertsubstances before use.

PREPARATION EXAMPLES Example 1

O,O-Diethyl O-(2-ethoxy-3-carbethoxy-4-quinolinyl) thiophosphate##STR5##

5.6 g (0.05 mol) of potassium tert.-butylate are suspended in 150 ml ofabsolute acetonitrile, and 13 g (0.05 mol) of2-ethoxy-3-carbethoxy-4-hydroxyquinoline are added. The mixture isstirred at 50° C. for about 30 minutes. After 9.4 g (0.05 mol) ofO,O-diethylthiophosphoryl chloride have been added, the reaction mixtureis stirred at 50°-60° C. for 5 hours and is then concentrated in vacuo.The residue is taken up in 200 ml cf toluene and the mixture isextracted by stirring successively with 100 ml of water, 100 ml of 1 Nsodium hydroxide solution and another 100 ml of water. The organic phaseis dried with sodium sulfate. After the solvent has been distilled offin vacuo, 17.2 g of O,O-diethyl-O-(2-ethoxy-3-carbethoxy-4-quinolyl)thiophosphate with a refractive index of n_(D) ²³ of 1.5452 areobtained.

The following compounds are obtained in an analogous manner: ##STR6##

                                      TABLE                                       __________________________________________________________________________    Example                                                                       No.  R.sup.1                                                                              R.sup.2                                                                           R.sup.3 R.sup.4                                                                           R.sup.5                                                                            X Physical data                              __________________________________________________________________________    2    OC.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   H    O n.sub.D.sup.31.5 : 1.5252                  3    S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   H    O n.sub.D.sup.22 : 1.5459                    4    S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   H    S n.sub.D.sup.23 : 1.5723                    5    CH.sub.3                                                                             C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   H    S n.sub.D.sup.28 : 1.5622                    6    C.sub.2 H.sub.5                                                                      CH.sub.3                                                                          COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   H    S melting point:                                                                63-67%                                     7    C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   H    S n.sub.D.sup.31.5 : 1.5533                  8    C.sub.2 H.sub.5                                                                      i-C.sub.3 H.sub.7                                                                 COOC.sub. 2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                   H    S n.sub.D.sup.27.5 : 1.5503                  9    S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOCH.sub.3                                                                           C.sub.2 H.sub.5                                                                   H    O n.sub.D.sup.21 : 1.5532                    10   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOCH.sub.3                                                                           C.sub.2 H.sub.5                                                                   H    S n.sub.D.sup.20 : 1.5747                    11   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COO--n-C.sub.3 H.sub.7                                                                C.sub.2 H.sub.5                                                                   H    O                                            12   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COO--n-C.sub.3 H.sub.7                                                                C.sub.2 H.sub.5                                                                   H    S                                            13   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COO--i-C.sub.3 H.sub.7                                                                C.sub.2 H.sub.5                                                                   H    O n.sub.D.sup.21 : 1.5445                    14   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COO--i-C.sub.3 H.sub.7                                                                C.sub.2 H.sub.5                                                                   H    S n.sub.D.sup.25 : 1.5648                    15   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    CH.sub.3                                                                          H    O n.sub.D.sup.21 : 1.5588                    16   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    CH.sub.3                                                                          H    S n.sub.D.sup.24 : 1.5808                    17   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    n-C.sub.3 H.sub.7                                                                 H    O n.sub.D.sup.21 : 1.5452                    18   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    n-C.sub.3 H.sub.7                                                                 H    S n.sub.D.sup.23 : 1.5649                    19   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    i-C.sub.3 H.sub.7                                                                 H    O                                            20   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    i-C.sub.3 H.sub.7                                                                 H    S                                            21   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   CONH--C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   H    O                                            22   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   CONH--C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   H    S                                            23   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   CONH--i-C.sub.3 H.sub.7                                                               C.sub.2 H.sub.5                                                                   H    O                                            24   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   CONH--i-C.sub.3 H.sub.7                                                               C.sub.2 H.sub.5                                                                   H    S Oil                                        25   S--C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                   COON(CH.sub.3).sub.2                                                                  C.sub.2 H.sub.5                                                                   H    O                                            26   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub. 5                                                                  COON(CH.sub.3).sub.2                                                                  C.sub.2 H.sub.5                                                                   H    S                                            27   S--CH.sub.3                                                                          C.sub.2 H.sub.5                                                                   COON(C.sub.2 H.sub.5).sub.2                                                           C.sub.2 H.sub.5                                                                   H    O                                            28   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COON(C.sub.2 H.sub.5).sub.2                                                           C.sub.2 H.sub.5                                                                   H    S                                            29   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   CN      C.sub.2 H.sub.5                                                                   H    O n.sub.D.sup.20 : 1.5732                    30   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   CN      C.sub.2 H.sub.5                                                                   H    S n.sub.D.sup.23 : 1.5879                    31   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   Cl      C.sub.2 H.sub.5                                                                   H    O                                            32   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   Cl      C.sub.2 H.sub.5                                                                   H    S                                            33   OC.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                   H       C.sub.2 H.sub.5                                                                   H    S n.sub.D.sup.31.5 : 1.5529                  34   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   H       C.sub.2 H.sub.5                                                                   H    O n.sub.D.sup.19 : 1.5647                    35   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   H       C.sub.2 H.sub.5                                                                   H    S n.sub.D.sup.23 : 1.5855                    36   C.sub.2 H.sub. 5                                                                     C.sub.2 H.sub.5                                                                   H       C.sub.2 H.sub.5                                                                   H    S n.sub.D.sup.31.5 : 1.5626                  37   NH--i-C.sub.3 H.sub.7                                                                C.sub.2 H.sub.5                                                                   H       C.sub.2 H.sub.5                                                                   H    S melting point:                                                                55-58° C.                           38   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   8-Cl O n.sub.D.sup.21 : 1.5623                    39   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   7-Cl O n.sub.D.sup.20 : 1.5598                    40   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   7-Cl S n.sub.D.sup.20 : 1.5765                    41   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   6-Cl O melting point:                                                                49-50° C.                           42   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   6-Cl S n.sub.D.sup.20 : 1.5743                    43   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   5-Cl O n.sub.D.sup.20 : 1.5627                    44   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   5-Cl S n.sub.D.sup.20 : 1.5763                    45   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   7-Br O n.sub.D.sup.20 : 1.5662                    46   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   7-Br S n.sub.D.sup.20 : 1.5852                    47   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   6-Br O n.sub.D.sup.21 : 1.5712                    48   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   6-Br S n.sub.D.sup.20 : 1.5862                    49   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   7-NO.sub.2                                                                         O melting point:                                                                59-68° C.                           50   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   7-CH.sub.3                                                                         O                                            51   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub. 2 H.sub.5                                                                  7-CH.sub.3                                                                         S                                            52   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   6-CH.sub.3                                                                         O n.sub.D.sup.20 : 1.5513                    53   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   6-CH.sub.3                                                                         S n.sub.D.sup.20 : 1.5688                    54   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   7-OCH.sub.3                                                                        O                                            55   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   7-OCH.sub.3                                                                        S                                            56   S--n-C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   7-CF.sub.3                                                                         O n.sub.D.sup.21 : 1.5183                    57   Phenyl C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   H    O                                            58   Phenyl C.sub.2 H.sub.5                                                                   COOC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   H    S                                            __________________________________________________________________________

FORMULATION EXAMPLES Example a

An emulsifiable concentrate is obtained from 15 parts by weight ofactive compound, 75 parts by weight of cyclohexanone, as the solvent,and 10 parts by weight of oxyethylated nonyl phenol (oxyethylated with10 mols of ethylene oxide), as the emulsifier.

Example b

A wettable powder which is readily dispersible in water is obtained bymixing 25 parts by weight of active compound, 64 parts by weight ofactivated salicic acid, as the inert substance, and 10 parts by weightof calcium lignin-sulfonate and 1 part by weight of sodiumoleyl-methyl-taurate, as the wetting agent and dispersing agent, andgrinding the mixture in a pinned disc mill.

Example c

A dusting agent is obtained by mixing 10 parts by weight of activecompound and 90 parts by weight of talc, as the inert substance, andcomminuting the mixture in an impact mill.

Example d

Granules consist, for example, of about 2-15 parts by weight of activecompound and 98-85 parts by weight of inert granular materials, such as,for example, attapulgite, pumice and quartz sand.

BIOLOGICAL EXAMPLES Example I

Field beans (Vicia faba) heavily infested with courpea aphid (Aphiscraccivora) were sprayed with an aqueous suspension of a wettable powderconcentrate containing 0.0125% by weight of the active compound fromExample 3, until the suspension drips off. The plants were placed in agreenhouse, and 100% destruction of the test animals was detected 3 daysafter the treatment. The compounds according to Examples 4, 33 and 35proved to be equally effective.

Example II

Bean plants (Phaseolus vulgaris) heavily infested with two-spottedspider mites (Tetranychus urticae normal-sensitive) were sprayed with anaqueous solution of a wettable powder concentrate containing 0.0125% byweight of the active compound from Example 3, until the suspensionstarts to drip off. A microscopic check 8 days after the treatmentshowed that all the stages of the population had been killed. Whentested in the same manner, the compounds according to Examples 4, 33,34, 35, 36 and 37 proved to be equally effective.

Example III

Red cotton bugs (Oncopeltus fasciatus) were sprayed with aqueousdilutions of wettable powder concentrates (in each case 0.025% by weightof active compound in the spray liquor) of the active compounds fromExamples 1, 33, 36 and 37 until dripping wet. The bugs were then placedin containers with lids which were permeable to air. The mortality wasevaluated 5 days after the treatment, and was 100% in each individualcase.

Example IV

1 ml of the compound to be tested (Example 3) was uniformly applied, asthe active compound in acetone with a concentration of 0.0125% byweight, to the inside of the lid and of the bottom of a Petri dish bymeans of a pipette, and the dish was left open until all of the solventhad evaporated. 10 houseflies (Musca domestica) were then placed intoeach Petri dish, the dishes were closed with the lids, and 100%destruction of the test animals was found after 3 hours.

The compounds according to Examples 36 and 37 proved to be equallyeffective.

Example V

As described in Example IV, the compound from Example 3 was uniformlyapplied, as the active compound in acetone with a concentration of0.025% by weight, to the inside of the lid and of the bottom of a Petridish, and the solution was allowed to dry. 10 larvae (L 4) of the Germancockroach (Blatella germanica) were then placed in each Petri dish, thedishes were closed with the lids, and 100% destruction of the testanimals was found after 72 hours.

The compound according to Example 36 proved to be equally effective.

Example VI

Cotton leaves (Gossypium sp.) were sprayed (600 l of spray liquor/ha)with an aqueous emulsion of the compound according to Example 3 in anactive compound concentration of 0.025% by weight, and caterpillars (10specimens, L 3-4 stage) of the cotton worm (Prodenia litura) which hadbeen likewise treated were placed on the cotton leaves. The leaves andcaterpillars were together placed in observation cages, and 100%destruction of the test animals was found after 48 hours. The compoundsaccording to Examples 34, 35 and 4 proved to be equally effective.

Example VII

Cabbage leaves (Brassica oleracea) were sprayed, as described in ExampleVI, with an aqueous emulsion of the compound according to Example 3 in aconcentration of 0.0125% by weight, and caterpillars (10 specimens, 3-4stage) of the diamond-back moth (Plutella xylostella) which had beenlikewise treated were placed on the leaves.

The leaves and caterpillars were together placed in observation cages,and 100% destruction of the test animals was found after 48 hours.

Example VIII

Cabbage leaves were treated, as in Example VII, with the compound fromExample 3 and caterpillars (10 specimens, L 3-4) of the cabbage moth(Mamestra brassicae) which had been likewise treated were placed on theleaves, and the leaves and caterpillars were together placed inobservation cages. 100% destruction of the test animals was found after48 hours.

Example IX

Bean leaves (Phaseolus vulgaris) were treated with an aqueous emulsionof the compound from Example 3 in a concentration of 0.0125% by weight(relative to the active compound) and were placed in observation cageswith larvae of the Mexican bean weevil (Epilachna varivestis) which hadbeen treated in the same way. Evaluation after 48 hours showed 100%destruction of the test animals.

The compounds according to Examples 4 and 35 proved to be equallyeffective.

Example X

Rice plants in the 4-leaf stage were sprayed until dripping wet with thecompounds given in Table I in concentrations of 1000, 500, 250 and 125mg of active compound/liter of spray liquor. After the spray coating haddried on, the plants were uniformly sprayed with a spore suspension ofPiricularia oryzae and were placed in a climatically controlled chamberat 25° C. and 100% relative atmospheric humidity for 48 hours. Theplants were then kept in a greenhouse at 25° C. and 85% relativeatmospheric humidity, and, 14 days after the inoculation, wereinvestigated for Piricularia oryzae infection. The degree of infectionwas expressed in % of infected leaf area, relative to the untreated,infected control plants (=100% infection).

                  TABLE I                                                         ______________________________________                                                   Area of leaf infected with Piricularia                                        oryzae in %, at                                                    Compound     1000   500        250  125                                       according    mg of active compound/liter of spray                             to Example   liquor                                                           ______________________________________                                        2            0      0          0-3  3                                         3            0      0          0    0                                         Untreated in-       100                                                       fected plants                                                                 ______________________________________                                    

The excellent fungicidal action of the compounds claimed againstPiricularia oryzae can be seen from Example X.

Example XI

Wheat plants were treated with the compounds claimed in Table II in useconcentrations of 1000, 500, 250 and 125 mg of active compound/liter ofspray liquor. After the coating of active compound had dried on, theplants were inoculated with spores of brown rust of wheat and wereplaced, dripping wet, in a climatically controlled chamber at 20° C. and100% relative atmospheric humidity. 24 hours later, the plants werereturned to a greenhouse and, 14 days after the inoculation, wereinvestigated for brown rust of wheat infection. The degree of infectionwas expressed in % of infected leaf area, relative to the untreated,infected control plants (=100% infection). Table II shows the goodaction of the compounds investigated.

                  TABLE II                                                        ______________________________________                                                   % leaf area infected with brown rust at                            Compound     1000   500        250  125                                       according    mg of active compound/liter of spray                             to Example   liquor                                                           ______________________________________                                        3            0      0          0    0                                         37           0      0          0-3  3                                         36           0      0          0-3  3                                         2            0      0          0    0                                         34           0      0          0-3  0                                         Untreated in-       100                                                       fected plants                                                                 ______________________________________                                    

Example XII

The compound claimed was uniformly mixed and distributed into soil whichhad been uniformly and heavily contaminated with Pythium ultimum. Thesoil thus treated was filled into plastic posts, and 10 pea seeds werethen sown into each pot. 8-10 days after sowing, the tests wereevaluated by determining the number of emerged, healthy plants andcalculating the degree of action of the compound claimed. Potscontaining infected, untreated soil served as controls.

                  TABLE III                                                       ______________________________________                                        Compound     Degree of action in % for                                        according    200    100        50   25                                        to Example   mg of active compound/kg of soil                                 ______________________________________                                        34           100    100        100  70                                        Untreated    0                                                                infected soil                                                                 ______________________________________                                    

We claim:
 1. A compound of the formula I ##STR7## in which R¹ denotes(C₁ -C₄)-alkyl, (C₁ -C₄)-alkoxy, (C₁ -C₄)-alkylmercapto, (C₁-C₄)-alkylamino, (C₁ -C₄)-dialkylamino or phenyl, R² denotes (C₁-C₄)-alkyl, R³ denotes hydrogen, halogen, COOalkyl, CONH(alkyl) orCON(alkyl)₂ with in each case 1-4 C atoms per alkyl radical, or cyano,R⁴ denotes (C₁ -C₄)-alkyl, R⁵ denotes hydrogen, halogen, nitro, (C₁-C₄)-alkyl, (C₁ -C₄)-alkoxy or trihalogenomethyl and X denotes oxygen orsulfur.
 2. O-ethyl-O-(2-ethoxy-3-carbethoxy-4-quinolinyl) S-n-propylthiophosphate.
 3. An insecticidal, acaricidal or fungicidal compositioncontaining an insecticidally, acaricidally or fungicidally effectiveamount of a compound defined in claim 1 and a customary formulationauxiliary.
 4. An insecticidal, acaricidal or fungicidal compositioncontaining an insecticidally, acaricidally or fungicidally effectiveamount of the compound of claim 2 and a customary formulation auxiliary.5. A method for combatting insects, acarids or fungi which comprisescontacting insects, acarids or fungi with an insecticidally,acaricidally or fungicidally effective amount of a compound defined inclaim
 1. 6. A method for combatting insects, acarids or fungi whichcomprises contacting insects, acarids or fungi with an insecticidally,acaricidally or fungicidally effective amount of the compound of claim2.